EP1125919A2 - (Méth)acrylate d'hydroxyalkyle stabilisé - Google Patents
(Méth)acrylate d'hydroxyalkyle stabilisé Download PDFInfo
- Publication number
- EP1125919A2 EP1125919A2 EP00128268A EP00128268A EP1125919A2 EP 1125919 A2 EP1125919 A2 EP 1125919A2 EP 00128268 A EP00128268 A EP 00128268A EP 00128268 A EP00128268 A EP 00128268A EP 1125919 A2 EP1125919 A2 EP 1125919A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxyalkyl
- acrylate
- meth
- carboxylate
- alkylene glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 125000002768 hydroxyalkyl group Chemical group 0.000 title claims abstract description 72
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 40
- -1 alkylene glycol Chemical compound 0.000 claims abstract description 79
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 58
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 claims description 11
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- BEKXVQRVZUYDLK-UHFFFAOYSA-N 2-hydroxyethyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCCO BEKXVQRVZUYDLK-UHFFFAOYSA-N 0.000 claims description 3
- SFAMKDPMPDEXGH-UHFFFAOYSA-N 2-hydroxyethyl propanoate Chemical compound CCC(=O)OCCO SFAMKDPMPDEXGH-UHFFFAOYSA-N 0.000 claims description 3
- BYSIMEBHZXYDGO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylpropanoate Chemical compound CC(C)C(=O)OCCCO BYSIMEBHZXYDGO-UHFFFAOYSA-N 0.000 claims description 3
- DOUBAFNWVFAWEC-UHFFFAOYSA-N 3-hydroxypropyl acetate Chemical compound CC(=O)OCCCO DOUBAFNWVFAWEC-UHFFFAOYSA-N 0.000 claims description 3
- AYIRHANHVDOYDJ-UHFFFAOYSA-N 3-hydroxypropyl propanoate Chemical compound CCC(=O)OCCCO AYIRHANHVDOYDJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 description 36
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 21
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 9
- 241000482268 Zea mays subsp. mays Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000003112 inhibitor Substances 0.000 description 6
- 230000002401 inhibitory effect Effects 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 230000000087 stabilizing effect Effects 0.000 description 6
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002195 synergetic effect Effects 0.000 description 5
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 3
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 3
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical class CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 2
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229950000688 phenothiazine Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- UZFMOKQJFYMBGY-UHFFFAOYSA-N 4-hydroxy-TEMPO Chemical group CC1(C)CC(O)CC(C)(C)N1[O] UZFMOKQJFYMBGY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UBUCNCOMADRQHX-UHFFFAOYSA-N N-Nitrosodiphenylamine Chemical compound C=1C=CC=CC=1N(N=O)C1=CC=CC=C1 UBUCNCOMADRQHX-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- IXPUJMULXNNEHS-UHFFFAOYSA-L copper;n,n-dibutylcarbamodithioate Chemical compound [Cu+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC IXPUJMULXNNEHS-UHFFFAOYSA-L 0.000 description 1
- OBBCYCYCTJQCCK-UHFFFAOYSA-L copper;n,n-diethylcarbamodithioate Chemical compound [Cu+2].CCN(CC)C([S-])=S.CCN(CC)C([S-])=S OBBCYCYCTJQCCK-UHFFFAOYSA-L 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- OWFXIOWLTKNBAP-UHFFFAOYSA-N isoamyl nitrite Chemical compound CC(C)CCON=O OWFXIOWLTKNBAP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LXCJGJYAOVCKLO-UHFFFAOYSA-N n-cyclohexyl-n-hydroxynitrous amide Chemical compound O=NN(O)C1CCCCC1 LXCJGJYAOVCKLO-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/04—Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/62—Use of additives, e.g. for stabilisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
Definitions
- the present invention relates to a stabilized hydroxyalkyl (meth)acrylate.
- Hydroxyalkyl (meth)acrylate is very high in reactivity and is easily polymerized, and hence it is general to stabilize hydroxyalkyl (meth)acrylate by adding polymerization inhibitor in its manufacturing process, storage or transportation.
- polymerization inhibitor hitherto, various compounds have been used, including phenol compounds such as hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2,4-dimethyl-6-tert-butyl phenol, and hydroquinone monomethyl ether, or para-phenylene diamines such as N-isopropyl-N'-phenyl-para-phenylene diamine, N-(1,3-dimethyl butyl)-N'-phenyl-para-phenylene diamine, N-(1-methyl heptyl)-N'-phenyl-para-pheny
- hydroxyalkyl (meth)acrylate is very likely to be polymerized.
- products of hydroxyalkyl (meth)acrylate contain impurities, including water, alkylene chlorohydrin, alkylene glycol di(meth)acrylate, dialkylene glycol mono(meth)acrylate, dialkylene glycol di(meth)acrylate, trialkylene glycol mono(meth)acrylate, trialkylene glycol di(meth)acrylate, (meth)acrylic acid dimer, hydroxyalkyl- ⁇ -acryloyloxy propionate, dialkylene glycol- ⁇ -acryloyloxy propionate, reaction materials such as (meth)acrylic acid and alkylene oxide, and others, in a range of several ppm to several percent, and they act to promote polymerization of hydroxyalkyl (meth)acrylate.
- an object of the present invention is to sufficiently stabilize the hydroxyalkyl (meth)acrylate in spite of its easily polymerizable property.
- the present inventors diligently studied to solve the above problems. As a result, the inventors have completed the present invention by finding that, by adding a specific ester compound and/or glycol compound to the phenol compound hitherto used as polymerization inhibitor, the stabilizing effect upon the easily polymerizable hydroxyalkyl (meth)acrylate is considerably enhanced as compared with conventional cases.
- a stabilized hydroxyalkyl (meth)acrylate contains a hydroxyalkyl saturated-carboxylate and/or alkylene glycol along with a phenol compound.
- the present invention is characterized by achieving the stabilization of the hydroxyalkyl (meth)acrylate by using the hydroxyalkyl saturated-carboxylate and/or alkylene glycol jointly with the phenol compound.
- the phenol compound used in the present invention is a phenol compound conventionally and generally used as polymerization inhibitor, and preferable examples thereof include hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2,4-dimethyl-6-tert-butyl phenol, and hydroquinone monomethyl ether. These may be used either alone respectively or in combinations with each other.
- the hydroxyalkyl saturated-carboxylate and/or alkylene glycol used together with the phenol compound in the present invention is a compound which characterizes the technical concept of the present invention.
- the hydroxyalkyl saturated-carboxylate preferably include hydroxyethyl acetate, hydroxyethyl propionate, hydroxyethyl isobutyrate, hydroxypropyl acetate, hydroxypropyl propionate, and hydroxypropyl isobutyrate. These may be used either alone respectively or in combinations with each other.
- As the alkylene glycol preferably, ethylene glycol, propylene glycol and others may be used. These may also be used either alone respectively or in combinations with each other.
- the amount of the phenol compound as used is preferably in the range of 0.001 to 0.5 wt % of hydroxyalkyl (meth)acrylate, and preferably 0.005 to 0.1 wt %. If less than 0.001 wt %, the polymerization inhibitory effect is not enough, or if more than 0.5 wt %, it is not economical.
- the amount of the hydroxyalkyl saturated-carboxylate and/or alkylene glycol as used is preferably in the range of 0.0001 to 2 wt %, more preferably 0.001 to 2 wt %, and still more preferably 0.01 to 1 wt %, of hydroxyalkyl (meth)acrylate. If less than 0.0001 wt %, the polymerization inhibitory effect is not enough, or if more than 2 wt %, it is not economical.
- the mixing rate of hydroxyalkyl saturated-carboxylate and/or alkylene glycol to phenol compound is not particularly limited, and each should be contained at the above rate in the hydroxyalkyl (meth)acrylate, and the blending rate by weight of the hydroxyalkyl saturated-carboxylate and/or alkylene glycol to the phenol compound is preferably in the range of 0.1 to 100 times, more preferably 1 to 80 times. If less than 0.1 times or more than 100 times, it is not preferred because the feature of the present invention, that is, the synergistic effect by combined use of hydroxyalkyl saturated-carboxylate and/or alkylene glycol with phenol compound is decreased.
- the hydroxyalkyl saturated-carboxylate and/or alkylene glycol as well as the phenol compound is allowed to coexist with the hydroxyalkyl (meth)acrylate, but, if aromatic hydrocarbon and/or aliphatic hydrocarbon is also allowed to coexist with the hydroxyalkyl (meth)acrylate, the polymerization inhibitory effect upon hydroxyalkyl (meth)acrylate is enhanced.
- the aromatic hydrocarbon is not particularly limited, but is preferably at least one member selected from the group consisting of benzene, toluene, and xylene.
- the aliphatic hydrocarbon is not particularly limited, but is preferably at least one member selected from the group consisting of hexane, heptane, and octane.
- the amount of the aromatic hydrocarbon and/or aliphatic hydrocarbon as added is preferably in the range of 0.0001 to 1 wt %, more preferably 0.0001 to 0.1 wt %, of hydroxyalkyl (meth)acrylate. If less than 0.0001 wt %, the polymerization inhibitory effect is not enough, or if more than 1 wt %, it is not economical.
- the method of adding phenol compound, hydroxyalkyl saturated-carboxylate and/or alkylene glycol, and, if necessary, aromatic hydrocarbon and/or aliphatic hydrocarbon, for stabilization of hydroxyalkyl (meth)acrylate is not particularly limited, but, for example, in the manufacturing process of hydroxyalkyl (meth)acrylate, they may be added together with the raw materials, or may be added in the distillation tower in the refining process.
- hydroxyalkyl saturated-carboxylate may be formed in the reaction solution, or by adding water at the time of reaction, alkylene glycol may be produced. It is also possible to add preliminarily before storage or transportation of hydroxyalkyl (meth)acrylate.
- the phenol compound, hydroxyalkyl saturated-carboxylate and/or alkylene glycol, and, if necessary, aromatic hydrocarbon and/or aliphatic hydrocarbon may be either added simultaneously, or added independently.
- hydroxyalkyl saturated-carboxylate when adding phenol compound and hydroxyalkyl saturated-carboxylate and/or alkylene glycol, in the manufacturing process of hydroxyalkyl (meth)acrylate, together with the raw materials at the time of reaction, or adding in the distillation tower in the refining process, depending on the thermal condition at the time of reaction or distillation, hydroxyalkyl saturated-carboxylate may be hydrolyzed or alkylene glycol may be dehydrated between molecules.
- the process solution in the manufacturing process for hydroxyalkyl (meth)acrylate for example, the reaction solution, distillation bottom liquid, distillate, or product may be lowered in concentration of hydroxyalkyl saturated-carboxylate and/or alkylene glycol in the process solution, and the feature of the present invention, that is, the synergistic effect by combined use of hydroxyalkyl saturated-carboxylate and/or alkylene glycol with phenol compound is not expressed, and sufficient stabilizing effect is not expected.
- examples of the method for analyzing the concentration of the remaining hydroxyalkyl saturated-carboxylate and/or alkylene glycol include analysis by GC (gas chromatography).
- This stabilizing agent may be preferably used.
- This stabilizing agent contains the hydroxyalkyl saturated-carboxylate and/or alkylene glycol along with the phenol compound, and is preferably used in the present invention.
- the phenol compound used in the stabilizing agent is, same as mentioned above, the phenol compound generally used hitherto as polymerization inhibitor, preferably including hydroquinone, methyl hydroquinone, tert-butyl hydroquinone, 2,6-di-tert-butyl parahydroquinone, 2,5-di-tert-butyl hydroquinone, 2,4-dimethyl-6-tert-butyl phenol, and hydroquinone monomethyl ether. These may be used either alone respectively or in combinations with each other.
- the hydroxyalkyl saturated-carboxylate usable in the stabilizing agent preferably includes, same as mentioned above, hydroxyethyl acetate, hydroxyethyl propionate, hydroxyethyl isobutyrate, hydroxypropyl acetate, hydroxypropyl propionate, and hydroxypropyl isobutyrate. These may be used either alone respectively or in combinations with each other.
- the alkylene glycol usable in the stabilizing agent preferably includes, same as mentioned above, ethylene glycol and propylene glycol. These may also be used either alone respectively or in combinations with each other.
- the stabilizing agent comprises phenol compound and hydroxyalkyl saturated-carboxylate and/or alkylene glycol and is used to stabilize the hydroxyalkyl (meth)acrylate, and the blending rate of the hydroxyalkyl saturated-carboxylate and/or alkylene glycol to the phenol compound is preferably in the range of 0.1 to 100 times, more preferably 1 to 80 times, by weight. If less than 0.1 times or more than 100 times, it is not preferred because the feature of the present invention, that is, the synergistic effect by combined use of hydroxyalkyl saturated-carboxylate and/or alkylene glycol with phenol compound is decreased.
- the stabilizing agent contains both phenol compound and hydroxyalkyl saturated-carboxylate and/or alkylene glycol and, if the phenol compound are mixed with hydroxyalkyl saturated-carboxylate and/or alkylene glycol in the above rate, the content of each component in the stabilizing agent is not particularly limited, but is preferably as follows: the content of the phenol compound is in the range of 0.1 to 90.0 wt %, and the content of the hydroxyalkyl saturated-carboxylate and/or alkylene glycol is in the range of 1.0 to 99.9 wt %, and the content of other additives is in the range of 0 to 90.0 wt %.
- the stabilizing agent may further contain other additives, as required, in addition to phenol compound and hydroxyalkyl saturated-carboxylate and/or alkylene glycol.
- additives include, for example, phenothiazine, or para-phenylene diamines such as N-isopropyl-N'-phenyl-para-phenylene diamine, N-(1,3-dimethyl butyl)-N'-phenyl-para-phenylene diamine, N-(1-methyl heptyl)-N'-phenyl-para-phenylene diamine, N,N'-diphenyl-para-phenylene diamine, and N,N'-di-2-naphthyl-para-phenylene diamine, or amine compounds such as thiodiphenylamine, or copper dialkyl dithiocarbamates such as copper dibutyl dithiocarbamate, copper diethyl dithiocarbamate, and copper dimethyl dithi
- the stabilizing agent may further contain aromatic hydrocarbon and/or aliphatic hydrocarbon in addition to phenol compound and hydroxyalkyl saturated-carboxylate and/or alkylene glycol.
- aromatic hydrocarbon is not particularly limited, but is preferably at least one member selected from the group consisting of benzene, toluene, and xylene.
- aliphatic hydrocarbon is not particularly limited, but is preferably at least one member selected from the group consisting of hexane, heptane, and octane.
- the rate of the aromatic hydrocarbon and/or aliphatic hydrocarbon to the phenol compound is preferably in the range of 0.0001 to 10 times, preferably 0.0001 to 1 times. If less than 0.0001 times or more than 10 times, the synergistic effect by combined use of the aromatic hydrocarbon and/or aliphatic hydrocarbon is less, which is not preferred.
- the present invention can sufficiently stabilize the hydroxyalkyl (meth)acrylate in spite of its easily polymerizable property.
- the hydroxyethyl acrylate used in the examples is a refined product from which the stabilizing agent has been removed.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether and 0.1 g of hydroxyethyl acetate were added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured, but the polymerization did not occur even after 130 hours.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether and 0.05 g of ethylene glycol were added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was not observed until 125 hours passed.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether and 0.01 g of hydroxyethyl acetate were added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was not observed until 100 hours passed.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether, 0.01 g of hydroxyethyl acetate, and 0.1 g of toluene were added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was not observed until 119 hours passed.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether and 0.5 g of hydroxyethyl acetate were added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 90 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was not observed until 402 hours passed.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether was added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was observed after only 65 hours.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.1 g of hydroxyethyl acetate was added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was observed after only 16 hours.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of phenothiazine and 0.1 g of hydroxyethyl acetate was added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 100 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was observed after only 73 hours.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.03 g of hydroquinone monomethyl ether was added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 90 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was observed after 235 hours.
- hydroxyethyl acrylate 100 g was placed into a glass container, and then 0.5 g of hydroxyethyl acetate was added. Immediately after this addition, the container was immersed into an oil bath as adjusted to 90 °C, and the time to initiate a polymerization was measured. As a result, popcorn polymerization of hydroxyethyl acrylate in the container was observed after only 38 hours.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymerisation Methods In General (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP36515499 | 1999-12-22 | ||
| JP36515499 | 1999-12-22 |
Publications (4)
| Publication Number | Publication Date |
|---|---|
| EP1125919A2 true EP1125919A2 (fr) | 2001-08-22 |
| EP1125919A3 EP1125919A3 (fr) | 2003-02-05 |
| EP1125919B1 EP1125919B1 (fr) | 2008-12-10 |
| EP1125919B2 EP1125919B2 (fr) | 2016-12-28 |
Family
ID=18483563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00128268.0A Expired - Lifetime EP1125919B2 (fr) | 1999-12-22 | 2000-12-22 | (Méth)acrylate d'hydroxyalkyle stabilisé |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US6706208B2 (fr) |
| EP (1) | EP1125919B2 (fr) |
| KR (1) | KR100447522B1 (fr) |
| DE (1) | DE60041036D1 (fr) |
| TW (1) | TW538020B (fr) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013131818A1 (fr) * | 2012-03-05 | 2013-09-12 | Evonik Röhm Gmbh | (méth)acrylmonomères stabilisés |
| EP3904327A1 (fr) | 2020-04-30 | 2021-11-03 | Röhm GmbH | Procédé de fabrication d'esters d'acide hydroxyalkyl(méth)acrylique par clivage oxydatif d'acétals de la méthacroléine |
| WO2022243038A1 (fr) | 2021-05-19 | 2022-11-24 | Röhm Gmbh | Procédé de préparation d'un composé susceptible de subir une polymérisation |
| WO2023169863A1 (fr) | 2022-03-08 | 2023-09-14 | Röhm Gmbh | Procédé de préparation de (méth)acrylates de haute pureté |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6770219B2 (en) * | 2002-10-15 | 2004-08-03 | Nalco Energy Services | Composition and method for preventing fouling in (meth)acrylic acid processes |
| DE602006018532D1 (de) | 2006-03-24 | 2011-01-05 | Postech Acad Ind Found | Stationäre phase und säule unter verwendung von cucurbiturilgebundenem kieselgel, und verfahren zur abtrennung von taxol unter verwendung der säule |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3399229A (en) * | 1965-04-03 | 1968-08-27 | Cassella Farbwerke Mainkur Ag | Process for the production of hydroxyalkyl esters of the alpha, beta-unsaturated carboxylic acids |
| US3804884A (en) * | 1972-12-07 | 1974-04-16 | Dow Chemical Co | Esterification process and catalyst therefor |
| US4368320A (en) * | 1980-07-23 | 1983-01-11 | Degussa Aktiengesellschaft | Process for the production of a hydroxyl group containing ε-caprolactone modified (METH) acrylate resin |
| EP0620206A1 (fr) * | 1993-04-15 | 1994-10-19 | Nippon Shokubai Co., Ltd. | Procédé d'inhibition de la polymérisation d'acide (méth-)acrylique et de ses esters |
| EP0763518A1 (fr) * | 1995-09-14 | 1997-03-19 | Nippon Shokubai Co., Ltd. | Méthode de stabilisation d'un composé vinylique contenant un procédé hydroxy et composition contenant un tel composé vinylique |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS4878119A (fr) | 1972-01-25 | 1973-10-20 | ||
| SE403771B (sv) | 1972-04-10 | 1978-09-04 | Continental Can Co | Forfarande for framstellning av en eteniskt omettad beta-hydroxiester genom omsettning av en polyepoxid med en omettad karboxylsyra |
| US4049731A (en) * | 1975-07-14 | 1977-09-20 | Ici United States Inc. | Stabilized polymerizable compositions |
| US4198238A (en) * | 1978-06-22 | 1980-04-15 | Hercules Incorporated | Photopolymerizable composition |
| JPS5846496A (ja) | 1981-09-14 | 1983-03-17 | 株式会社小松製作所 | 計測デ−タの伝送システム |
| EP0189987B1 (fr) * | 1985-01-25 | 1992-04-29 | Imperial Chemical Industries Plc | Compositions d'uréthane polymérisables |
| DE3513779A1 (de) * | 1985-04-17 | 1986-10-23 | Merck Patent Gmbh, 6100 Darmstadt | Stabilisierte loesungen strahlungsvernetzbarer polymervorstufen hochwaermebestaendiger polymere |
| US5258423A (en) * | 1990-03-26 | 1993-11-02 | Rohm And Haas Company | Stabilization of methacrylic polymers against sterilizing radiation |
| US6102205A (en) * | 1997-10-08 | 2000-08-15 | Medlogic Global Corporation | Prepolymer compositions comprising an antimicrobial agent |
| JP2001064278A (ja) * | 1999-08-26 | 2001-03-13 | Tokuyama Corp | 含硫黄（メタ）アクリレート系重合性単量体 |
-
2000
- 2000-12-01 US US09/728,179 patent/US6706208B2/en not_active Expired - Lifetime
- 2000-12-04 TW TW089125812A patent/TW538020B/zh not_active IP Right Cessation
- 2000-12-20 KR KR10-2000-0078958A patent/KR100447522B1/ko active IP Right Review Request
- 2000-12-22 EP EP00128268.0A patent/EP1125919B2/fr not_active Expired - Lifetime
- 2000-12-22 DE DE60041036T patent/DE60041036D1/de not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3399229A (en) * | 1965-04-03 | 1968-08-27 | Cassella Farbwerke Mainkur Ag | Process for the production of hydroxyalkyl esters of the alpha, beta-unsaturated carboxylic acids |
| US3804884A (en) * | 1972-12-07 | 1974-04-16 | Dow Chemical Co | Esterification process and catalyst therefor |
| US4368320A (en) * | 1980-07-23 | 1983-01-11 | Degussa Aktiengesellschaft | Process for the production of a hydroxyl group containing ε-caprolactone modified (METH) acrylate resin |
| EP0620206A1 (fr) * | 1993-04-15 | 1994-10-19 | Nippon Shokubai Co., Ltd. | Procédé d'inhibition de la polymérisation d'acide (méth-)acrylique et de ses esters |
| EP0763518A1 (fr) * | 1995-09-14 | 1997-03-19 | Nippon Shokubai Co., Ltd. | Méthode de stabilisation d'un composé vinylique contenant un procédé hydroxy et composition contenant un tel composé vinylique |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013131818A1 (fr) * | 2012-03-05 | 2013-09-12 | Evonik Röhm Gmbh | (méth)acrylmonomères stabilisés |
| CN104159955A (zh) * | 2012-03-05 | 2014-11-19 | 赢创罗姆有限公司 | 稳定化的(甲基)丙烯酸类单体 |
| US9206112B2 (en) | 2012-03-05 | 2015-12-08 | Evonik Roehm Gmbh | Stabilized (meth)acrylic monomers |
| EP3904327A1 (fr) | 2020-04-30 | 2021-11-03 | Röhm GmbH | Procédé de fabrication d'esters d'acide hydroxyalkyl(méth)acrylique par clivage oxydatif d'acétals de la méthacroléine |
| WO2021219409A1 (fr) | 2020-04-30 | 2021-11-04 | Röhm Gmbh | Procédé de production d'esters d'acide hydroxyalkyl(méth)acrylique par dédoublement oxydatif d'acétals de méthacroléine |
| WO2022243038A1 (fr) | 2021-05-19 | 2022-11-24 | Röhm Gmbh | Procédé de préparation d'un composé susceptible de subir une polymérisation |
| WO2023169863A1 (fr) | 2022-03-08 | 2023-09-14 | Röhm Gmbh | Procédé de préparation de (méth)acrylates de haute pureté |
Also Published As
| Publication number | Publication date |
|---|---|
| TW538020B (en) | 2003-06-21 |
| KR100447522B1 (ko) | 2004-09-08 |
| KR20010057573A (ko) | 2001-07-04 |
| EP1125919B1 (fr) | 2008-12-10 |
| DE60041036D1 (de) | 2009-01-22 |
| US20010006226A1 (en) | 2001-07-05 |
| EP1125919A3 (fr) | 2003-02-05 |
| US6706208B2 (en) | 2004-03-16 |
| EP1125919B2 (fr) | 2016-12-28 |
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